Flotation recovery of mirabilite from salt complexes

ABSTRACT

Sulfonated alkenes, sulfonated unsaturated petroleum fractions and fatty acids serve as collector reagents for the forth flotation of mirabilite from salt complexes, particularly a mirabilite-natron salt complex.

United States Patent Chemtob et al. {4 1 Aug. 22, 1972 541 FLOTATION RECOVERY OF 2,442,455 6/1948 Booth ..209/166 MIRABILITE FROM SALT 2,310,315 3/1943 Pye ..219/166 COMPLEXES 3,461,159 8/1969 Wendt ..260/513 R 3,525,434 8/1970 Garret ..209/166 [72] Inventors: Elie M. Chemtob, Claremont; R0-

lando V. Marcote, La Verne, both of lf. Ca Primary Examiner-Frank W. Lutter [73] Assignee: Occidental Petroleum Corporation Assistant Examine,- RObert fl l r [22] g 6 Att0rneyChristie, Parker & Hale [21] Appl. No.: 848,070

52 us. Cl. ..209/166 [57] ABSTRACT [51] Int. Cl. ..B03d 1/02 Sulfonated alkenes, Sulfonated unsaturated petroleum 58 Field of Search ..209/166, 167 fractions and fatty acids serve as collector reagents for the forth flotation of mirabilite from salt complexes, 56] Referencs Cited particularly a mirabilite-natron salt complex.

UNITED STATES PATENTS 1,968,876 8/ 1934 Crago ..209/ 166 X 11 Claims, No Drawings FLOTATION RECOVERY OF MIRABILITE FROM SALT COMPLEXES BACKGROUND OF THE INVENTION been expensive and inefficient.

SUMMARY OF THE Invention It has now been found that froth flotation in an aqueous media can be utilized for the separation of mirabilite from salt mixtures, particularly natron (Na CO l H O)-mirabilite N a SO 'l0I-I O) salt systems, when there is used as the collector reagent a sulfonated hydrocarbon containing at least about eight carbon atoms, a fatty acid containing at least about eight carbon atoms or a salt of a fatty acid containing at least about eight carbon atoms.

DESCRIPTION According to the present invention sulfonated hydrocarbons are provided as reagents for the flotation separation of mirabilite from mirabilite-natron salt complexes.

As used in the practice of this invention, the term sulfonated hydrocarbon means sulfonated alkenes, particularly sulfonated a-olefins and sulfonated unsaturated petroleum fractions, which are otherwise unsubstituted. Generally, the sulfonated hydrocarbons should contain at least about eight carbon atoms, preferably from about 12 to about 30 carbon atoms,

and more preferably from about 20 to about 30 carbon atoms. The sulfonated hydrocarbons can be obtained by the sulfonation of the corresponding naturally occurring alkenes, naturally occurring a-olefins, a-olefins obtained by the polymerization of the lower a-olefins such as ethylene and propylene under controlled conditions, and unsaturated petroleum fractio ns having on an average from about eight to about 30 or more carbon atoms in the extracted molecules with sulfur trioxide in a manner set forth in French Pat. No. 1,419,652 and British Pat. specification No. 983,056, incorporated herein by reference. Illustrative, but nowise a limiting of the sulfonated hydrocarbons useful in the practice of this invention, include sulfonated pentenes, hexenes, heptenes, octenes, nonenes, decenes, undecenes, dodecenes, tridecenes, tetradecenes, pentadecenes, hexadecenes, octadecenes, nondecenes, eicosenes, heneicosenes, doeicosenes, trieicosenes, tetraeicosenes, pentaeicosenes, hexaeicosenes, octaeicosenes and like alkenes as obtained from natural and polymerization sources. The source of the hydrocarbon may be refined or crude and can contain minor amounts of other constituents which do not affect beneficiation. The amount of sulfonated hydrocarbon used as a collector reagentis not narrowly critical and can range from about 50 to about 2,000 grams, preferably from about 500 to about 1,000 grams, per ton of salt processed.

The fatty acids used as the collector reagent in the practice of this invention are saturated and unsaturated straight chain fatty acids containing about eight, preferably from about 12 to about 22 or more, carbon atoms in the chain. Illustrative, but nowise a limiting of the fatty acids which may be used in the practice of this invention are caprylic, lauric, myristic, palmitic, stearic, oleic, linoleic, linolenic, arachidic, behenic, coco oil, tall oil and like fatty acids. The fatty acids may be used in a purified state or in a crude state as a mixture.

The fatty acid salts used in the practice of this invention are normally obtained by the neutralization of the crude fatty acids with sodium hydroxide, potassium hydroxide, ammonia and like bases.

To assist the collectors employed in this invention, there may also be present in the flotation system, secondary and tertiary alcohols or mixtures thereof. The nature and the quantity of the secondary or tertiary alcohol is not narrowly critical and there may be mentioned, as illustrations of useful secondary and tertiary alcohols; methylethyl carbinol, i-butyl alcohol, trimethyl carbinol, 2,4-dimethyl-3-ethyl-3-hexanol, methyl amyl alcohol, di-isobutyl carbinol, 2,6,8- trimethyl-4-nonanol, secondary amyl alcohol, tertiary amyl alcohol, methyl isobutyl carbinol and like secondary and tertiary alcohols. When used as assisting agents, the secondary or tertiary alcohols are normally present in an amount of from about 50 to'about or more grams per ton or ore solids processed.

Flotation separations of mirabilite from salt mixtures containing mirabilite and natron can be conveniently carried out using conventional flotation equipment and procedures at temperatures from about 12 C to aboub 30 C without loss of the crystal identity of the salts to be separated. Where a low temperature flotation separation is desired, it is merely required to provide the flotation equipment with ordinary refrigeration cooling means to maintain the processed salt within the temperature range desired. Equipment useful in the flotation separation of mirabilite from mirabilitenatron salt complexes, using the reagent collectors of this invention, include, among others, Denver and Wemco flotation systems.

The flotation separation of mirabilite, according to the present invention, can be effectively carried out at slurry solid contents up to about 40 percent by weight or more, although it is preferred for efficiency to carry out the flotation at a salt solids content between about 20 to 30 weight percent. The salts may be conveniently treated as obtained from the source. However, it is preferred to wash the salts to remove organics and bitterns which can reduce the efficiency of the collector reagent employed.

It is also within the ambit of this invention to separate mirabilite from more complex salt mixtures such as those containing mirabilite, natron, halite, borax and other minor sodium salts. In such systems, sulfonated hydrocarbons or fatty acids are used to separate, by flotation, a mirabilite rich constituent from a natron rich constituent and other flotations using different reagents may be used to fractionate the natron and mirabilite respectively from the rough constituents.

3,685,652 3 4 The following examples are illustrative of the flota- EXAMPLE 4 tion separations which can be carried out according to the practice of this invention A salt mixture containing 50 percent by weight mirabilite and 50 percent by weight natron was suspended EXAMPL 1 5 in a liquor containing 10.0 sodium sulfate and 15.0 percent sodium carbonate at a slurry density of 25 percent. The-mixture of salts was separated in a Denver Cell using as the collector Petronate HL, a sulfonated petroleum fraction having a molecular weight range from 440 to 470 and an empirical formula of C H SO Na and manufactured and sold by Sonneborn Division of Witco Chemical Company. At a concentration equivalent to 200 grmas per ton of salt solids, a float containing 90 percent mirabilite and percent natron and a residue composition containing 61.4 percent mirabilite and 39.6 percent natron was obtained.

A binary mixture containing 55 percent by weight mirabilite and 45 percent by weight natron separated from a harvest of salts obtained by cooling Searles Lake brine to 5 C were slurried in a brine saturated with mirabilite and natron salts at a solids concentration of 10 25 percent by weight. Froth flotation separation was made using, as the flotation collector, a-eicosene in an amount equivalent to 500 grams per ton of salt solids processed. The flotation was carried out at a temperature between about 5 and 20 C in a Denver Cell.

There was obtained a float containing 72.0 weight percent mirabilite and 28.0 weight percent natron, en- EXAMPLE 5 trainment free, and a residue containing 44.6 weight percent mirabilite and 54.4 weight percent natron. In The Procedure of Example 4 was repeated except this separation 32.2 percent of the contained mirabilite that the Collector Concentration was increased in two was recovered successive portions to an equivalent of 250 grams per EXAMPLE 2 ton of salt solids. The first float had a composition of 97.1 percent mirabilite and 2.9 percent natron, and the Usmg the Procedure set forth for example 1 a salt second float had a mirabilite purity of 95 percent. The

gh p h comprlsihg mirabilite natron halite composition of the residue was 61.4 percent mirabilite tained in a crystallization of Searles Lake brine at 5 C and 396 percent natron was treated in a froth flotation apparatus using Witco LQCS, an aklyl aryl petroleum s ulfonate prepared by EXAMPLE 6 Witco Chemical Company, in a concentration equivalent to 700 grams per ton of salt solids The procedure of Example 4 was repeated except processed. Table 1 shows an analysis of the system bethat the collector concentration was increased to an fore and after flotation, in which there was a yield of equivalent of 650 grams per ton of salt solids. The compercent mirabilite from the salt system at a mirabilite position of the float obtained had 94.4 percent mirabe purity of 75.2 percent. and 5.6 percent natron by weight. The residue con- TABLE 1.-SYSIEM COMPOSITION Before flotation Composition of solids (percent) (entraln- Analysis (percent) ment free) w l t Weight of ions (gm.)

eigi Cl S0 C03 Natron Mirabilite (gms) Cl CO3 Feed solid 81 13. 5 ll. 0 48. 5 51. 5 500 4. 2 07.5 48. 0

Liquor -l. l5 4. 0 1, 526 G3. 4 68. 7 03. 8

Totals 2,020 67.6 13 .5 141.8

H jlTc r llbtntion A" Float (with Entruin1nent .07 10.1 5 5 24.8 75. 151 l 0 30.4 B .& Residue (with entraimnenty. .83 11.7 11 1 57.1 42.1! 334 2 8 3'.) .38 1 End liquor l. .2 4. 5 0 3 1, 104 0.5 8 07. 4 I4 .5

Totals 1, 071! 66. 6 130. 8 (1 EXAMPLE 3 7 5O tained 54.5 percent mirabilite and 48.5 percent natron by weight The float obtained in Exam 1e 2 was sub ected to a p 1 EXAMPLE 7 cleaner flotation using only the entrained collector as the flotation reagent. Table 11 contains an analysis of The procedure of Example 4 was repeated except the system before and after flotation in which there was that th re was used as the collector Petronate CR, a

obtained a mirabilite yield in the float of 67.5 percent. 5 lf t d petroleum fracti n having a molecular TABLE ll.SYS'll I1\l COMlUbl'llUN Before flotntlon Composition of solids (percent) (OIILCltllllb Analysis (percent inent free) Weight of ions (gun) WWW-V e Weight C1 S0; C0; Nntron Mirnbillte (gins) C1 S0; C0;

Feed solid. .ls'll .51. 3 l. l 10. 8 83. .5 405 3.715 .111. (1 10.1 Liqi|0r 1.27 -1. .5 [$.15 1,771 75.15 74.4 100.8 'l0l1ils' 15,1530 70,3 173. 1 128.1!

Alter flotation Flont (with entrainment). .00 .57 0 1. 13 .5. 7 117.3 .523 1 l (10. .5 i. .5 Residue (with ('llllflllllll lll). .x7 '51 5 4,151 17 1 x11, 131! l 5 .511. 1 5.14 End liquor -1. .5 1 1 (i. 3 1, x31; 77 .5 75. l 115.5

Totals... 2,1!1 717 1 15.0 124.5

weight between 490 and 510 and an empirical formula of C l-l SO Na and manufactured by Sonnebom Division of Witco Chemical Company, in a concentration equivalent to 1,000 grams per ton of salt solids. The float was determined to have a mirabilite concentration of 81.7 percent and a natron concentration of 18.3 percent by weight.

'EXAMPLE8 A salt grouping obtained by cooling Searles Lake brine'was subjectto flotation in a Denver Cell using as the collector Petronate HL in a concentration equivalent to 650 grams per ton of salt solids. The float had a mirabilite purity of 94.4 percent. An analysis of the system before and after flotation appears in Table Ill.

6 carbon atoms, fatty acids containing at elast about eight carbon atoms in the chain and salts of fatty acids containing at least about eight carbon atoms in the TABLE III.SYSTEM COMPOSITION Before flotation Composition of solids (percent) Analysis (percent) (entrainment free) Weight of ions (gm.)

Weight 01 S04 C00 Halite Mirabilite' Natron (gms.) 01 S04 CO1 Feedmhlmth mtramment) .282 10.41} Not determined 230.5 .68 40.5

Liquor 1.01 4.2 5.68 1,320 13.40 558 75.5

Totals 1,802.5 14.38 124.8 122.0

After flotation Floatentraimnentfiw fifulffijjj11:11: "if? .f'. 113 1111: 1 1 115 183;

Residue (entrainment free) 1 5.8 0. 85 53.0 47 0 1, 569

End liquor 0. 91 5. 1 0. 43 14. 4 80. 5 100. 1

Totals 1,802 14.4 122.35 119.28

EXAMPLE 9 The procedure of Example 8 was repeated except there was used as the collector Neofat 255, a stripped coco fatty acid chiefly containing groups having 12, 14, and 16 carbon atoms in the chain and manufactured by armor Chemical, in an amount equivalent to 100 grams per ton of salt solids processed and, as the promotor, methyl isobutyl carbonate in an amount equivalent to 100 grams per ton of salt solids processed. The float obtained had a composition of 68.7 percent mirabilite and 31.3 percent natron.

What is claimed is:

1. A process for the flotation of mirabilite from a mirabilite-natron salt complex which comprises subjecting the salt complex to froth flotation in an aqueous media in the presence of a beneficiating amount of a collector reagent selected from the group consisting of sulfonated hydrocarbons containing at least about eight 7. A process as claimed in claim 1 in which the sulfonated collector reagent is present in an amount equivalent to about 50 to about 2,000 grams per ton of salt solids processed.

8. A process as claimed in claim 1 in which the sulfonated collector reagent is present in an amount $27333 I v UNITED, STATES PATENT OFFICE CERTIFICATE OF Patent No. I Dated August 22, 1972 Inventor) Elie M. Chemtob et a l It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

1'- v i W In the Patent Col. 1, line 12, the word "drystall'ite.

should read -crystallite.-; line 14, omit the "e" between the words the and "components"; line 50, omit the space between the letters "0'' and "n" in the word "fractions". Col. .2, line 38, the word 'aboub" should read about Col 3, line 55, the figure 67.,5" should read -6-7.6-. Col. 4, line 5, insert the word "percent" between "10.0" and "sodium"; line 13, the word "grmas" should read "gramsline 33, the word "mirabe" should read --mirabi-lite-. Col. 5, line 39, the name "armor should read Armour--. Col.v 6, line 1, ,the word elast" should read "least-""- Signed and sealed this 8th day of May 1973.

(SEAL) Attest: 7 Y

' EDEN-EB 1.1 *"lTCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents 

2. A process as claimed in claim 1 in which the sulfonated hydrocarbon contains from about 12 to about 30 carbon atoms.
 3. A process as claimed in claim 1 in which the fatty acid or fatty acid salt contains from about 12 to about 22 carbon atoms.
 4. A process as claimed in claim 1 in which the sulfonated hydrocarbon is sulfonated Alpha -eicosene.
 5. A process as claimed in claim 1 in which the sulfonated hydrocarbon is an alkyl aryl petroleum sulfonate.
 6. A process as claimed in claim 1 in which the fatty acid is a coco fatty acid.
 7. A process as claimed in claim 1 in which the sulfonated collector reagent is present in an amount equivalent to about 50 to about 2,000 grams per ton of salt solids processed.
 8. A process as claimed in claim 1 in which the sulfonated collector reagent is present in an amount equivalent to about 500 to about 1,000 grams per ton of salt solids processed.
 9. A process as claimed in claim 1 in which the sulfonated hydrocarbon is selected from the group consisting of sulfonated alkenes and sulfonated petroleum fractions.
 10. A process as claimed in claim 9 in which the sulfonated alkene is a sulfonated Alpha -olefin.
 11. A process as claimed in claim 10 in which the Alpha -olefin contains from about 12 to about 30 carbon atoms. 